Fluorinated polyacrylates containing amino side chains for the surface modification of waterborne epoxy resin

Fluorinated polyacrylates containing amino side chains (FACAs) were synthesized to improve the water repellency of waterborne epoxy resin. First, FACA was prepared by a two-step process. Then, a phase-inversion emulsion technique, taking FACA as the reactive surface additives, was employed to prepare waterborne epoxy resin. The effect of the fluorinated content and the length of the fluorine side chain on the surface, thermal, and bulk properties of the waterborne epoxy resin were investigated. It was observed that moderate increase of the fluorinated content or the length of the fluorine side chain improved the contact angle and thermal properties while the mechanical property was not deteriorated. A small amount of fluoride (0.07 wt %) in the EA-F1/3-1 sample can dramatically increase the water contact angle from 72.63° to 95.31° due to the strong tendency of the macromonomers to migrate toward the outmost layer, resulting in enrichment of fluorine atoms on the surface. X-ray photoelectron spectroscopy results revealed that for a given weight of the two macromonomers, F atomic concentration of the copolymer modified by longer fluorinated side chains was higher than that modified by short fluorinated side chains. From the present investigation, FACA successfully improved the surface property of waterborne epoxy resin and showed a prominent potential application in large-scale industrialization. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47091.     

聚氨酯-聚丙烯酸酯共聚乳液的制备及形态研究

以聚醚二元醇(GE-210)、异佛尔酮二异氰酸酯(IPDI)和二羟甲基丙酸(DMPA)为主要原料,制备了水性聚氨酯(WPU)乳液;再采用丙烯酸丁酯(BA)和甲基丙烯酸甲酯(MMA)与WPU乳液共聚制备水性聚氨酯-聚丙烯酸酯(WPUA)复合乳液。讨论了WPUA乳液及胶膜的性能,并采用FT-IR、XRD、SEM和AFM等分析手段研究了WPUA涂膜的结构和形貌。结果表明,WPUA乳液具有良好的室温贮存稳定性及成膜性能,胶膜为无定型结构,透光率90%。与WPU乳液相比,WPUA乳液粒径有所增大,对基材的浸润性更好;其胶膜耐水性能明显提高;SEM和AFM分析同时显示,WPUA胶膜微观呈现"脊-谷"结构。     

含高相对分子质量氟化聚硅氧烷链段的水性聚氨酯脲的制备与性能(英文)

以数均相对分子质量(n)较高(8 361～21 760)的α,ω-二羟基聚甲基(3,3,3-三氟丙基)硅氧烷(PTFPMS)、聚酯二元醇、二羟甲基丙酸、异佛尔酮二异氰酸酯和乙二胺为原料,制备了一系列贮存稳定性优良的大分子主链中含有少量(质量分数为5%)长PTFPMS链段的聚氨酯脲(PUU)水分散液,并对其性能进行了研究.结果表明,与未改性或用低相对分子质量(n 为798)PTFPMS改性的PUU水分散液相比,用高相对分子质量PTFPMS改性的PUU水分散液的粒径减小;含高相对分子质量PTFPMS链段的PUU水分散液成膜后,其表面疏水性和力学性能比纯PUU水分散液有很大程度的提高,而比含低相对分子质量(n 为798)的PTFPMS链段的PUU水分散液有一定程度的提高.     

Effect of crosslinking on the surface free energy and surface reorganization of waterborne fluorinated polyurethane

To endow waterborne fluorinated polyurethanes (WFPUs), films with stable lower surface free energy and lower surface reorganization after the films contacted with water, a series of crosslinked WFPUs (CWFPUs) emulsions were prepared by adjusting the content of aziridine (AZ). The effect of crosslinking on the surface free energy, glass-transition temperature (T _g), water absorption, and surface composition of dry/hydrated WFPUs and CWFPUs films were studied by CAs test, dynamic mechanical analysis, water absorption measurements, and X-ray photoelectron spectroscopy. When the fluorine content was 0.5%, the surface free energy of the CWFPUs films modified by 0.4% AZ content (CWFPU-6-0.5-CK0.4) reached to the lowest value of 15.76 mN m⁻¹ which almost equaled to the surface free energy (15.45 mN m⁻¹) of the dry uncrosslinked films (WFPU-6-0.5). With the increasing of AZ content, the T _{g, hard} of hard segments of the CWFPUs films increased and the water absorption of the CWFPUs films decreased, which suggested the formation of the crosslinked network structures. The studies of the surface elements and groups composition of dry/hydrated WFPUs and CWFPUs both confirmed that the surface reorganization and the migration of fluorinated side chains were restricted by the crosslinked network structures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47167.     

不同官能度水性聚氨酯丙烯酸酯的合成及性能

以丙烯酸羟乙酯与季戊四醇三丙烯酸酯作为封端剂,分别合成了二官能度水性聚氨酯丙烯酸酯(WPUA2)和六官能度的水性聚氨酯丙烯酸酯(WPUA6),并用红外光谱、粒径仪、热重分析对合成产物结构和性能进行表征。研究表明,相比于使用低官能度WPUA2紫外光固化所得聚氨酯丙烯酸酯(PUA)涂膜,加入单体或使用多官能度WPUA6,都可使PUA固化膜凝胶率提高20%以上,吸水率降低30%;质量损失10%,分解温度增大82℃。提高预聚物官能度可有效提高涂膜交联密度和耐热性能,并具有与加入活性单体相似的应用效果。     

The Cu(I)-mediated azide–alkyne cycloadditions as a facile and efficient route for functionalization of waterborne polyurethane

The Cu(I)-mediated azide–alkyne cycloaddition reaction, “click” chemistry, has been used to functionalize the waterborne polyurethane, by which a novel fluorinated waterborne polyurethane (FWPU) was synthesized. FWPU was confirmed by FT-IR and ¹H NMR. The structure and properties of FWPU were characterized by water contact angle, water absorption, surface energy, scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometry (EDS), thermogravimetric analysis (TGA) and X-ray diffraction (XRD), etc. From the research of the surface properties, it was found that the modified materials were endowed with a remarkable hydrophobicity and stain resistance. SEM results showed that the micro-phase separation of FWPU became increasingly apparent with the rise of fluorinated side chains in polyurethane backbone. XRD measurements reflected that the crystallinity of FWPU tended to decrease firstly and then increase with the change of fluorine content. TGA results demonstrated that FWPU possessed flame retardant performance to a certain extent due to the incorporated alkyne groups in the FWPU to improve the final char strongly.     

长烷基链对水性聚氨酯在非极性基材上附着力的影响

以聚己二酸新戊二醇酯（PNA）、二聚酸聚酯多元醇（BY3026）、异佛尔酮二异氰酸酯（IPDI）为主要原料制备了一系列侧链含长链烷基的水性聚氨酯（WPU）乳液并制成胶膜。通过FTIR、DSC表征了胶膜的结构和热性能，测试了乳液粒径及胶膜的力学性能、吸水率、接触角以及其在双向拉伸聚丙烯薄膜（BOPP）上的附着力。结果表明，当m(BY3026)∶m(PNA)从0∶1增加到3∶5,WPU乳液粒径增大，胶膜的耐水性增强，表面能先减小后增大，拉伸强度和断裂伸长率从52.6 MPa和2607.2%分别降低至38.7 MPa和1911.2%。当m(BY3026)∶m(PNA)=2∶5时，制备的WPU胶膜表面能为35.43mJ/m2,WPU乳液在BOPP薄膜上的T-剥离强度为2.98 N/25 mm。     

水性油墨用室温自交联纯丙乳液的合成及应用

以甲基丙烯酸甲酯(MMA)、丙烯酸异辛酯(2-EHA)、甲基丙烯酸(MAA)、双丙酮丙烯酰胺(DAAM)为聚合单体,己二酰肼(ADH)为交联剂,采用半连续种子乳液聚合法合成软核硬壳结构的水性纯丙乳液。利用ATR-FTIR、TEM、GPC、TG、DMA表征水性纯丙乳液的结构和性能。结果表明:乳液成膜过程中DAAM中的—CO—与ADH中的—NHNH_2发生反应,交联度增加,提高了乳液膜的耐水性、热稳定性、玻璃化转变温度和油墨在双向拉伸聚丙烯(BOPP)薄膜上的附着力。当DAAM用量(以MMA和2-EHA的总质量为基准,下同)从0增加到2%,m(ADH)∶m(DAAM)=0.7∶1.0时,乳液膜的吸水率从24.2%降到7.6%,油墨的附着力从87%升至100%;当m(ADH)∶m(DAAM)从0∶1增加到0.7∶1.0,DAAM用量为2%时,乳液膜的吸水率从28.1%降至7.6%,油墨的附着力从0增至100%。当DAAM用量为2%,m(ADH)∶m(DAAM)为0.7∶1.0时,水性纯丙乳液可用作环保型水性油墨的连接料。     

超支化水性聚氨酯乳液的制备及性能研究

以顺丁烯二酸酐改性的超支化聚酯Boltorn H20、聚四氢呋喃2000和异佛尔酮二异氰酸酯为主要原料合成了超支化水性聚氨酯乳液,研究了改性超支化聚酯Boltorn H20的合成,以及改性超支化聚酯中羧基含量、初聚—NCO/—OH物质的量比、催化剂用量等对制备水性聚氨酯的影响,并探讨了亲水基团含量、乳化温度、中和度等因素对乳液及涂膜性能的影响,进一步使用傅里叶红外和热重分析分别对超支化聚氨酯涂膜的结构和热稳定性能进行了表征及测试。结果表明,在不加催化剂,初聚—NCO/—OH物质的量比为2∶1,亲水基团含量为2.05%的条件下,合成得到的含固量为30%的超支化水性聚氨酯乳液稳定性好。由此得到的超支化聚氨酯薄膜的耐水性和热稳定性较好。     

单组分自乳化水性环氧树脂的合成及其涂膜性能研究

用有机硅、甲基丙烯酸及其酯类单体接枝改性环氧树脂,合成了具有自乳化性能的水性环氧树脂乳液。用激光粒度分析仪测定乳液的粒径及其分布,用傅里叶红外、热重分析仪对聚合产物作了结构表征和热分析。考察了温度、引发剂用量对接枝率及接枝率对乳液成膜性能的影响;甲基丙烯酸、有机硅及单体总量对乳液稳定性、成膜物耐水性和耐盐水性的影响。结果表明:当配方选用引发剂、有机硅用量分别为单体总质量的5.5%、2.5%,m(单体总量)∶m(环氧树脂)=1∶2,丙烯酸及其酯类单体的玻璃化温度Tg为30℃,体系酸值为35 mgKOH/g,接枝温度为110℃时,制得的水性环氧树脂乳液具有良好的稳定性、耐水性及耐盐水性。     

全氟烷基侧链改性阳离子水性聚氨酯的制备与应用研究

以异佛尔酮二异氰酸酯(IPDI)、聚四氢呋喃二醇(PTMG1000)、1,4-丁二醇(BDO)、N-甲基二乙醇胺(MDEA)、三羟甲基丙烷(TMP)等为主要原料,通过全氟乙基辛醇(FEOH)封端改性,制备了含全氟烷基侧链的阳离子含氟水性聚氨酯乳液。通过红外光谱(FTIR)、热重分析(TG)对其结构与膜性能进行了表征,并且将其作为纸张防水防油剂用于表面施胶,对处理后纸张表面的水和液体石蜡接触角及纤维形态进行了研究。结果表明,聚氨酯分子链中的全氟烷基成膜时产生了较大取向作用,含氟基团向空气/聚合物界面伸展,有明显的"趋表"现象,这有利于形成低能表面,对聚合物内部分子形成了很好的保护作用,使涂膜具有较高的耐热降解性能。当表面施胶质量分数为0.3%时,纸张即可达到优异的防水防油效果,水接触角达到134.7°,液体石蜡接触角达到119.2°。     

环氧改性水性聚氨酯涂料印花粘合剂的研制

用环氧树脂改性水性聚氨酯(WPU)乳液来提高胶膜的耐水性、耐溶剂性、耐化学品性以及力学性能。讨论了环氧树脂的加入量和加入方式对乳液性能的影响。确定了水性聚氨酯乳液的制备工艺条件:nNCO/nOH=2:1,预聚温度65～70℃,反应2h;使用3.71%～4.63%的DMPA进行亲水改性,且DMPA要用N-甲基-2-吡咯烷酮溶解后加入;扩链时间2h;乳化温度<5℃。得到了共聚法制得的环氧树脂改性WPU性能较优、且环氧树脂加入量6%为宜的结论。     

聚碳酸酯型水性聚氨酯乳液的制备与性能

以聚碳酸酯二元醇和异佛尔酮二异氰酸酯为主要原料,采用预聚法合成了聚碳酸酯型水性聚氨酯( WPU) ,用傅里叶变换红外光谱表征了WPU,考察了不同NCO/OH( 摩尔比) 对WPU 乳液粒径及薄膜的耐水性、拉伸性能的影响,并研究了WPU 的热稳定性。结果表明,随着NCO/OH 值的增大,WPU乳液的粒径增大,稳定性降低,薄膜的耐水性和拉伸强度提高,扯断伸长率降低; WPU 薄膜的热分解速率较快,硬段的热分解温度为193 ℃,最大失重温度为287 ℃; 软段的热分解温度为321 ℃,最大失重温度为364 ℃左右。     

Preparation and photochromic properties of waterborne polyurethane containing spirooxazine groups

Two novel photochromic spirooxazines, SO 1 and SO 3, were successfully prepared and characterized by Fourier transform infrared spectroscopy (FTIR), ¹H-NMR, and mass spectrometry with electrospray ionization (ESI-MS). SO 1 was doped and grafted with waterborne polyurethane (WPU) to afford D₁-WPU and G₁-WPU. D₃-WPU was prepared by doping SO 3 with waterborne polyurethane. FTIR spectra indicated that SO 1 was grafted onto waterborne polyurethane successfully. Scanning electron microscopy proved that spirooxazines of D-WPU can be effectively dispersed in a waterborne polyurethane matrix, and spirooxazines of G-WPU are evenly distributed in the copolymer. The results showed that the light transmittance of modified waterborne polyurethane films decreased compared with pure waterborne polyurethane films, but the water resistance and tensile strength were better. Ultraviolet–visible spectra demonstrated that the thermal stability of spirooxazine derivatives improved significantly after being modified. The fading rate constant of the D₃-WPU film (k = 0.0079 s^-1) during the discoloration process decreased 9.77 times in contrast to SO 3 in ethanol, which showed that the thermal stability of spirooxazine in WPU film was obviously enhanced. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47067.     

高固含量水性聚氨酯分散体的合成

引　言水性聚氨酯是水溶型、水分散型和水乳化型聚氨酯的统称 .水性聚氨酯与溶剂型相比较 ,具有生产、运输和使用安全 ,不污染环境的优点 ,在涂料、黏合剂和皮革涂饰剂等方面的应用备受重视[1] ,成为近 10年来全世界的研究热点 .水性聚氨酯的弱点是其制成的涂料和涂饰剂的机械性能、耐水性不如溶剂型聚氨酯 .克服这些弱点 ,是近年来各国研究者努力的方向[2 ] .在改善水性聚氨酯性能方面有大量研究报道 ,诸如降低亲水基团含量 ,增大乳液粒径 ,采用强力机械分散增加乳液贮存稳定性 ,改善乳液对涂膜基材表面的润湿性、黏附力等等[3] .但很少见…     

Preparation of high hydroxyl self-emulsifying polyester and compounding with acrylate

Waterborne saturated polyester (WSP) with high hydroxyl content was prepared through solution polymerization by using stepwise feeding and stage heating methods. The stability of polyester dispersion was enhanced in terms of molecular structure and polymerization process. The conditions of polymerization process, monomer types, and catalyst type were determined. The effects of the ratio of alcohol-to-acid, trimethylolpropane (TMP) content and the feeding method, the content of terminal monomer and branched monomer on the dispersion were investigated. The stability of the self-emulsifying polyester and the water resistance of the film were proved to be excellent. Through transesterification, waterborne unsaturated polyester (WUP) was synthesized by WSP. Polyester-acrylate composite emulsion can be obtained by physical blending or chemical copolymerization of synthetic waterborne polyester. The viscosity of the composite emulsion was improved, and the hardness and water resistance were improved. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48278.     

Polyphosphazene nanotube and modified waterborne polyurethane prepared by in situ polymerization

Novel hybrid inorganic/organic poly[cyclotriphosphazene-co-(hexafluoroisopropylidene)] nanotubes (PZTs) were synthesized through nucleophilic substitution using one-step method. The surface of PZTs contains hydroxyl and fluorine groups with a ratio of approximately 1:3, which imparts many functional properties to the nanotubes. The introduction of the active hydroxyl groups increased the chemical bond crosslinking between the nanotubes and the matrix resin. The introduction of fluorine atom provided the hydrophobicity and abrasion resistance properties. The water contact angle of PZTs is 140.3°. Chemical reaction occurred between WPU and PZTs to form covalent bonds through in situ polymerization. The water contact angle and thermal stability of waterborne polyurethane (WPU)/PZTs increased with the increasing nanotube content. When the nanotube content was 1.0 wt%, the maximum tensile strength of the composites was 3.36 MPa and the maximum elongation-at-break was 446.8%. The nanotubes showed toughening and strengthening characteristics. When 1.0 wt% PZTs were incorporated, the friction coefficient and abrasion loss of the composites reached a minimum value. The addition of nanotubes could increase surface hardness and crosslinking degree, absorb the coating heat of friction, and reduce the adhesive wear of polymer and the wear amount. The introduction of fluorine atoms could form a chemical transfer membrane and reduce the friction coefficient. Polyphosphazene nanotubes showed excellent modification properties in the waterborne polyurethane system.

     

双酚AF改性水性聚氨酯的合成与性能研究

通过丙酮法以聚碳酸酯二元醇(PCDL)、异佛尔酮二异氰酸酯(IPDI)为原料,双酚AF为改性剂,2,2-二羟甲基丙酸(DMPA)、1,4-丁二醇(BDO)为扩链剂,三乙胺为中和成盐剂合成了一系列不同双酚AF含量改性的水性聚氨酯(WPU)乳液。通过傅立叶红外光谱(FTIR)、X射线衍射(XRD)、热重分析(TGA)、力学性能、表面水接触角、吸水率测试等对聚合物结构与性能进行了表征。结果表明,随着双酚AF含量的增加,WPU薄膜的表面水接触角增大,吸水率降低,耐水性能有所提高;薄膜拉伸强度与断裂伸长率先增大后降低。热重分析结果表明,WPU薄膜的热分解温度随着双酚AF添加量的增加先增大后降低,仍保持良好的耐热性能。XRD分析结果表明,改性前后的水性聚氨酯薄膜均为非晶型,双酚AF的加入对结晶性能并无影响。     

Maleopimaric acid‐modified two‐component waterborne polyurethane for coating applications

Maleopimaric acid (MPA), an important rosin derivative, was used to partially substitute isophthalic acid for the preparation of an anionic polyol (MPP) dispersion. The MPP dispersion was then applied to prepare a novel maleopimaric acid‐modified two‐component waterborne polyurethane (MPP‐2K‐WPU). The influences of NCO:OH molar ratio on the thermal properties, water absorption, surface free energy, and application properties of MPP‐2K‐WPU films were investigated. With increasing NCO:OH molar ratio, the thermal stability, pencil hardness, and ethanol resistance of MPP‐2K‐WPU films were improved, but the water resistance was enhanced firstly and then weakened. The surface free energy of MPP‐2K‐WPU films mainly depended on the dispersion interaction which was related to the structure of macromolecules. In addition, compared with the control sample of PP‐2K‐WPU(1.5:1) film, the MPP‐2K‐WPU(1.5:1) film exhibited improved thermal stability, water resistance, gloss, pencil hardness, and ethanol resistance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43292.     

PDMS改性蓖麻油基水性聚氨酯的制备及防污性能

本研究以低成本的二甲基二甲氧基硅烷为主要原料，通过水解缩合反应制备合成了聚二甲基硅氧烷（PDMS），进而将其引入蓖麻油基水性聚氨酯（CWPU-SOP）中制备了具有防污性能的蓖麻油基水性聚氨酯(PDMS/CWPU-SOP)。结果表明，当PDMS引入量为8%时，与CWPU-SOP薄膜相比，PDMS/CWPU-SOP薄膜接触角提高了25?，达110?，PDMS/CWPU-SOP薄膜的吸水率下降了7%，为15%；PDMS提高了薄膜疏水性和耐水性。PDMS/CWPU-SOP薄膜在不同酸碱性的液滴在其表面可自由滚落且不留痕迹，具有一定的防污性能。